Condensation products of the anthraquinone series



Patented N06. 28, 1933 ooNDENsATI oN PRODUCTS oF THE THRAQWONE SERIES Paul Nawiasky, Ludwigshafen-on-the lthine, and

Berthold Stein, Mannheim, Germany, assign-H ors to General Aniline Works, Inc., New York, N. Y., a eorporation of Delaware No Drawing.

Application February 17,- 1931;

Serial No. 516,506, and inGermany February f ,ljj solaims (or 260-60) I The present invention relates to new condensation products of the anthraquinone series which are considered to be l-amino-2.l-dianthrimides substituted in the amino group by an, aromatic dicarboxylic acid radicle and which are sap'onifiable to the free amines.

' pounds produced in this manner in practically We have found that new condensation products of the anthraquinone series which are especially important as initial materials forlthe manufacture and-production of dyestuffs are obtained. by condensing a lamino-ii-halogenanf thraquinone 'in which both OflihE hydrogen atoms of the amino "group are replacedby the carbonyl groupsof an aromatic dicarboxylic acid capable of forming a monomolecular anhydride, with a l-amino-anthraquinone.

Aromatic dicarboxylic acids of the aforesaid kind comprise, for example 'lphthalic acid, naphthalic acid, naphthalene- 125 and 2.3 -dic'arboxylic acid and derivatives ofthe said acids.:- The comquantitative yields are 1-amino-2.1-dianthrimides substituted in theamino group by an aromatic dicarboxylic radicle corresponding to the formula: V

inwhich the anthraquinone nuclei may be substituted and wherein R is an aromatic radicle in which the two 0:0 groups are attached in such positions that the corresponding dicarboxylic acid is capable of forming amonomolecular anhydride. I H

In order to produce from these imino-dianthrimides dyestuffs of the type: of N -'dihydro- 1.2.2.1'-anthraquinoneazine,- the aromatic di-,

carboxylic acid radicle must befsplit off. If at-- tempts, however, are made to split the dicarboxyl acid radicle ofi again this does not take place in the usual manner by employing strongly-acid or strongl alkaline saponifying'agentsac. i r

We have now found that the' dicarboxylic aci radicle may be split oifjfrom'thesaid' conden sation products by treating them with ammonia, its substitution products o'r similar agents having a mild alkaline action, such asfor example alkali a A metal ohen olates,{whilefh'eating. ThfLZ-diamino-anthraquinones substituted in the :nitro; en, atom in the '2-position thu obtainedfare' usually coloured substancesand are readilyfcon-j densed according to known methods'to 'form' dyestuffs ofthe N-dihydro-l.2.2;1'-anthraquinoneazine series. 7 I 1 1 The following examples will-further illustrate the nature of this invention, but the inventionis not restricted to these examples. The parts are by weight. j

Example 1.

l-amino-2 -bromanthraquinone with phthalic anhydride) are boiled in 300 parts of nitrobenzene with 23 partsvof l-aminoanthraquinone, 15 parts of anhydrous sodium acetate and 0.5 part of cop- J per acetate until l-aminoanthraquinone can no longer be detected. The reaction mixture is allowedto cool,- is; filtered by suction and the residueis treated with steam; A reaction product free froinhalogenwh'ich forms large dark'red crystals and 'yvhichdissolves in concentrated sub" 1 phuric acid giving "a deep. blue /col'ouration. is

obtained in excellent yields. The ."compound,\

after crystallization from nitrobenzene, contains '75.5 per cent of carbon a 3.3 per cent of hydrogen and, ,7 5.0 per cent of nitrogen according't o analysis.v These values agree very well with the calculatedjvalues for"1'-'phtha1imino= 2.1-di anthrimide viz: 'j- I 15.2 per cent of carbon g p j 3.2 per cent of hydrogen and 4.9 per cent of nitrogen, V

i'Exa mpZefZ I a e 110 parts; a spam in -z-asmaiit aqtm;

43 parts? "of 1 phthalimino-2-bromanthra- 'quinone I (obtainable forv example by heating one and v 85 parts of 1 -aminoe5,-benzoylaminol anthraquinone with an additionofAQ partsoi corresponding to the formula:

sodium acetate and 1 part of copper acetate are heated to boiling in 750 parts of nitrobenzene for some hours. After cooling, the red crystals which have separated out are filtered off by suction and the residue is washed with nitrobenzene, ethyl alcohol and water. In this manner 1- phthalimino 5-benzoylamino-Z.1'-dianthrimide manner sponding to the formula:

dissolves in concentrated sulphuric acid giving a green blue 'colouration.

is obtainedin a goodyield in theform, of copper redcry'stals. 1 It 'dissolvesin sulphuric acid giving a" dull violet colouration.

Example V 33y replacing the, 1 arnino-5-benzoy1aminoanthraquinone in Example 2 by b5 parts of l-amino- 4 methox-yanthraquinone, 1 phthalimino 4f methoxy-2.l-dianthrimide corresponding .to the f rm a v a I for'med inapracticallyQuantitative yields-and separates from the solu'tion in the form or lustrous violet rhomb ic crystals-when cooled It dissolves in vconcentrated sulphuric .acid giving a de p bme ca ulation i v Ear-21mm 5.5 parts of "515=diaminodiphthaloylcarbazole obtainable by warming 5;5--dibenz0ylimino-1.1'-

dianthrimidein. chlorosulphonic acid and saponiingsthe-resulting product bymeans of sulphuric acid, are heated while stirring with llvparts of 1-phthalimino-2-brornanthraquinone, 4 parts of g sodium acetate andOA-part of copper acetate in 100 parts oisci-1mg nitrobehzehe until unchanged 5.5--diaminodiphthaloylcarbazole can no longer be detected. The new condensation product, which is very difficulty soluble even in hot nitrobenzene; separates out during the reaction in the form of fi'nebr'own violet needles. The reaction product isworked up and isolated in the usual Example 5 parts of l-amino-3-chloroanthraquinone are The new compound probably corre heated to boiling with parts of l-phthalirnino- -2-bromoanthraquinone,'1 part of copper acetate,

40 parts of anhydrous sodiumacetate arid50'0 parts of nitrobenzene until the initial materials cannot anymore be detected. The reaction mixture is allowed to cool,- the precipitate. filtered off and freed from solvent and inorganic com ponents. Largebrown orange crystals of a product corresponding tothe formula:

are thus obtained. The new product dissolves in concentrated sulphuric acid'to give a blue solution which on warming turns yellow.-

I Example 6 quinone are heated to boiling for several hours with 165 parts of l-amino-B-benzoylanthraquinone (obtainable by eliminating the amino group from 1-brom0-4-aminoanthraquinone-3- carboxylic acid, converting the resulting product by means of thionylchloride into the acid chlo ride, condensing the latter with benzene with the aid of aluminium chloride and replacing the bromine atom by an amino group by heating with ammonia under pressure); '75 parts ofrsodium acetate and 3 .parts ofcopper ace'tatein 1000. parts of nitrobenz'ene The precipitate is filtered ofi'and freed from solvent and inorga-nic'f com- 'ponents' in the usual mannen The 1-'phthal-- 220 parts of 1-phtha11m1no-2-bromanthraim in 0-3 benzoyl ll"-di'anthrimide tained corresponds to the formula:

thus I ob- It f orms beautiful, uniform red'crystals dissolve ing in concentrated sulphuric acid to give adeep blue solution which on standing changes its color to a pure yellow. i

I Example 7 50 parts of the condensation product from 1- phthalimino-2-bromanthraquinone and l-arninoanthraquinone prepared. according toExample 1 are heated for 6 hours at 180 C. with 1000 parts of 20 per cent ammonia in an iron autoclave After cooling, the product is'filtered oil by suction and washedv with Water. 1amino-2.1-dianthrimide is obtained in good yields in the form of fine currant brown needles.

Example 8 10 parts of the dianthrimide obtainable bythe condensation of 1 aminoanthraquinone-B-carboxylic acid ethyl ester with 1-phthalimino-2 bromanthraquinone (forming brownred crystals dissolving inconcentrated sulphuric acid to give a blue solution) are heated for a short time to from" to 120, C. while stirring with 2mm of hydrazine hydrate in.50 parts of nitrobenzene. In this manner, with temporary dissolution and simultaneous splitting off of the 'phthaloyl radicle, the red crystals change into violet needles. After cooling, the needles are filtered off by suction, treated with steam and boiled with dilute caustic soda solution to remove the hydrazine salt formed. The ethyl ester of 1-amino-2.1dian'- thrimide-3'-carboxylic acid thus obtainable which corresponds to the formula:

. v I 0 dissolves in concentrated sulphuric acid to give a steel-blue colouration. When warmed the solution becomes a beautiful yellow green colour.

Example 9 10 parts of the condensation product from 1 -phthalimino 2 bromanthraquinone and 'lamino-4.para-toluidoanthraquinone are heated in 100 parts of nitrobenzene together with 6 parts of ethylene diamine hydrate for a short anthrimide' corresponding to the I formula I V which probably corresponds to the formula:

time to from 160 to 180 C. .under a re fiuxjcon- 1 denser while stirring. When the ture is. cooled, 1-amino-4 .para-toluido-Zl' -diseparates out in the form Example 8. Thenew compound dissolves in concentrated sulphuric acid to give a bl'ue colouration'. I V

Example 10 f -12 parts of the condensation product 'from" inoanthraquinone are suspended in- 120 iparts."

potassium l -phthalimino-2-bromanthraquinone and l-amof nitrobenzene and 5 parts of reaction mixof green blue needles. The working up is carried out as described in Phenolate are added. The Whole is then heated toi'rom 150 to 160? CVwhile stirring well, where-- by the splitting off of the phthaloyl radicletakes place in a short time. The working up is carried out'as described "in Example 8. f Example 11 V 10 parts of the condensation product from 2 molecular proportions of I bromanthraquinone and 1 molecular proportion of 4.4-dianiinodiphthaloylcarbazole 1 are heated l-phthaliiniho-Z to boiling in 300 parts of nitrobenzene with 5" parts of hydrazine hydrate until the completion of the 'saponification. This may be ascertained when from a sample a product separates out on cooling giving adull blue solution in concentrated sulphuric acid even when warmed, in

contradistinction to the initial material the blue colouration of dissolution of which in sulphuric acid changes to yellow when swarmed. The whole is then allowed to cool and therproduct is filtered oil? by suction and treated with steam 1 consisting of halogen, thearnino; benzoylamino, toluido; benzoyl, alkyloxy, carboxylic acid includ- 2.1'-dianthrimide corresponding to the forto remove the nitrobenzene. mula:-

What we claim is:- V I O 1; Condensation products of the 'anthraquinone u series which are probably 1-im'ino-2.1-dianthrimides corresponding to the formula:

V N--H o N n u 0:0 (1:0 H O I 0 N s I 0 K forming dark red crystals dissolving in concentrated sulphuric acid to give a deep blue solution.

B 4. The condensation product, of the anthraquinone series which probably is 1-phtha1imino-' 3 benzoyl-2.1'-dianthrimide' corresponding to ll the formula: i

in which the anthraquinone nuclei may be sub stituted by a substituent selected from the group consisting of halogen, the amino, benzoylamino; toluido, benzoyl, alkyloxy, carboxylic acid ineluding: esterified carboxylic acid groups and 'members of a carbazol nucleus, and wherein'R,

is a benzene or a naphthalene radicle to which the two 0:01 groups are attached in such positions that the corresponding dicarboxylic acid is capable of forming a monomolecular anhydride. i

2. Condensation products of the anthraquinone series which are probably 1-phthalimino-2.1-' dianthrimides corresponding to the formula: V Y

forming uniform red crystalsdissolving in concentrated sulphuric acid to givea deep blue s0- 0 lution which on standing changes its color to a ll pure yellow.

' '5. The condensa quinone series which probably is l-phthalimino- 3'-ch1oro-2.1-dianthrimide corresponding :to the A N I formula:

H o=c (3:0

,in which the anthraquinone; nuclei may be substituted by a substituent selected from the group 5 forming brown orange crystals dissolving in con ing esterified carboxylic acid groups and memcentrated sulphuric acid to give a blue solution bers of a carbazol nucleus. which on warming turns yellow.

3. The condensation product or" the anthra- PAUL NAWIASKY. quinone series which probably is 1-phthalimino- BERTHOLD STEIN. I:

ion product of the 'anthra- 

